US3335205A - Phosphonate purification process - Google Patents
Phosphonate purification process Download PDFInfo
- Publication number
- US3335205A US3335205A US370660A US37066064A US3335205A US 3335205 A US3335205 A US 3335205A US 370660 A US370660 A US 370660A US 37066064 A US37066064 A US 37066064A US 3335205 A US3335205 A US 3335205A
- Authority
- US
- United States
- Prior art keywords
- phosphonate
- phosphite
- halogen
- alkyl
- contaminant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims description 13
- 238000000746 purification Methods 0.000 title description 6
- -1 PHOSPHONATE DIESTER Chemical class 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 29
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 17
- 239000000356 contaminant Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 description 17
- 229910052801 chlorine Inorganic materials 0.000 description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 15
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 12
- 230000000875 corresponding effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LXGWTNCMXZCXRM-UHFFFAOYSA-N (4-methyl-2,3-diphenylphenyl) dihydrogen phosphite Chemical compound C=1C=CC=CC=1C=1C(C)=CC=C(OP(O)O)C=1C1=CC=CC=C1 LXGWTNCMXZCXRM-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910020667 PBr3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- CASMCKLJGNCLNZ-UHFFFAOYSA-N ethyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCC)OC1=CC=CC=C1 CASMCKLJGNCLNZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
Definitions
- This invention relates to a process for the purification of organic phosphonates.
- this invention relates to a process for the purification of alkyl phosphonate diesters contaminated with halogen-containing impurities.
- this invention relates to a method for removing chlorine from a monoalkyl phosphonic acid diester containing as a contaminant corresponding chloromonalkyl phosphonic acid diester.
- plasticizers for polymeric films and resins
- organic phosphorus compounds such as tricresyl phosphate, or alkyl phosphonates such as decyl dicresyl phosphonate
- materials useful as plasticizers should be free from halogen contamination since this halogen has a strong tendency to cause discoloration or yellowing in the plasticized polymer. This problem is especially important when the plasticized polymer is white or clear.
- monoalkyl phosphonic acid diesters contaminated with corresponding chloromonoalkyl phosphonic acid diesters can be substantially dehalogenated and made suitable for use as plasticizers by treatment with phosphite triesters, as more particularly described hereinafter. While phosphites have been used directly as antioxidants and stabilizers for polymeric resins, it was not at all apparent that these materials would be effective for the purpose herein intended, especially since one of the most reactive commercial phosphite triesters, triethyl phosphite, proved ineffective.
- an object of the present invention to provide a process for the purification of alkyl phosphonate diesters contaminated with halogen-containing impurities.
- the present invention is concerned with a process for the substantial removal of a halogen selected from group Cl, Br and I from an alkyl phosphonate diester containing as a contaminant corresponding haloalkyl phosphonate diester which involves treating the contaminated alkyl phosphonate diester in the liquid phase, preferably at atmospheric pressure, at a temperature of at least 200 C. for a period of from about 1 to about 10 hours, with at least a stoichiometric amount, based upon contaminant, of a phosphite triester having a boiling point higher than the temperature at which treatment is effected.
- a halogen-containing compound that boils under the ambient conditions of the treatment.
- the formula designated '1. represents the monoalkyl phosphonate diesters which are to be purified and which may be prepared as described in copending application Serial No. 223,511 referred to hereinbefore.
- the formula designated II represents the contaminant, or corresponding halomonoalkyl phosphonate diester.
- I and II represent the mixture treated in accordance with the process of the present invention.
- the formula designated III represents the phosphite triester which reacts with the halogen-containing contaminant in what is believed to be an Arbuzov-type reaction.
- Formula IV represents one of the products resulting from the reaction between II and III and can be classed generally as an alkyl ibisphosphonate diester. If desired, this product can be separated from I by distillation or the like. However, IV is also a phosphonate and it can be retained in admixture with I for use as a plasticizer, since the deleterious halogen has been removed.
- Formula V represents the organic halide by-product resulting from the reaction between II and III. Product V preferably should be removed by volatilization from the reaction mixture as it forms.
- V is an alkyl halide, it, too, would react with the phosphite triester in an Arbuzov reaction, and, thus, interfere with the desired reaction. If V is an aromatic halide, it will not undergo the Arbuzov reaction and need not be removed as it forms. However, it must eventually be removed from the product by volatilization.
- R is an alkyl hydrocarbon radical having from 1 to 23 carbon atoms.
- alkyl radicals include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and eicosyl.
- the alkyl phosphonate diester may be a mixture wherein R may be of varying lengths since; as pointed out in the co-pending application, SerialNo. 223,511, this portion of the.
- X in Formulas Hand V is a halide selected from the group consisting of chlorine, bromine and iodine. Thepreferred and most common halide is chlorine.
- R in Formulas I, II and IV is an organic radical selected from the group consisting of aliphatic hydrocarbon, cycloaliphatic hydrocarbon, aromatic hydrocarbon, mixed aliphatic-aromatic hydrocarbon such as alkaryl and aralkyl groups and alkyl oxyalkylene.
- hydrocarbon radicals may besaturated or unsaturated and substituted or unsubstituted, but when substituted they must be substituted with inert functional groups, that is, those groups which will not interfere with the reaction between the halogen impurity and the phosphite triester.
- R groups include methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, and the like; olefinic and acetylenic analogues of the foregoing; cyclohexyl, cyclopen tyl, methylcy'clohexyl, phenyl, methylphenyl, ethylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, tolyl, xylyl, methoxyethyl, ethoxyethyl, methylpolyoxyethyl, methoxypropyl, eth lpolyoxypropyl, and the like.
- Typical products represented by Formula I include ethyl dicresyl phosphonate, octyl dicresyl phosphonate, ethyl dioctyl phosphonate, octyl diphenyl phosphonate, pentyl dibutyl phosphonate and the like.
- Formula II represents cor-responding compounds having a halogen attached to the carbon atom alpha to the phosphorus atom in the phosphonate diester.
- Eormula III represents the phosphite triester employed in the process of the present invention.
- this phosphite triester must be carefully chosen. That is, it must have a boiling point higher than about 200 C. and above the temperature at which the process is employed. Further, it must contribute a radical, R", which when combined with the halide, X, results in a product which boils below the temperature at which the process is carried out.
- R" is an organic radical selected from the group consisting of aliphatic hydrocarbon, cycloaliphatic hydrocarbon and aromatic hydrocarbon. All of the R" may be different or alike, but in any event, the triphosphite ester must meet.
- the preferred phosphite triester is triphenyl phosphite.
- Typical phosphites which may be employed include trioctyl phosphite, tricresyl phosphite, octyldicresyl phosphite, ethyldiphenyl phosphite, ethyldicresyl phosphite, octylnonyldecyl phosphite, diphenylcresyl phosphite, ethyldinaphthyl phosphite, octyldicyclohexyl phosphite, and the like.
- 'Phosphite esters are, in general, prepared by treating hydroxyl-containing organic compounds such as alcohols, phenols, etc., with phosphorus trihalides such as PCl 'PBr3 and P1
- hydroxyl-containing organic compounds such as alcohols, phenols, etc.
- phosphorus trihalides such as PCl 'PBr3 and P1
- solvents may be employed, but they are generally not preferred since they tend to diminish the reaction rate by the dilution factor involved. However, if solvents are employed, they should be high boiling, viz, boil in excess of 200 C. and be inert in the environment.
- the process of the present invention is preferably carried out at atmospheric pressure, although higher or lower pressuremay be employed provided the reactants are kept in the liquid phase and the temperature is maintained above about 200 C. and may go as high as the boiling pointof the lowest boiling reactant.
- the process may be carried out over a period of about 1 to about hours. It will be appreciated that the nature of the material being treated and. the choice of reactants will have a bearing, within the limits above prescribed, .on the conditions to be employed in carrying out the process.
- an 1 alkyl phosphonate diester containing as a contaminant an amount, up to about 40% by weight, preferably between about 5 and about 10% by weight of corresponding haloalkyl phosphoate diester is admixed with at least a stoichiometric amount, based upon the amount ofcontaminant of a phosphite triester having a boiling point of at least about 200 C.
- the alkyl phosphonate diester can be octyldicresyl phosphonate containing chlorooctyldicresyl phosphonate as a contaminant and the phosphite triester can be triphenyl phosphite.
- the mixture is maintained in the liquid phase at atmospheric pressure and at a temperature of at least 200 0, preferably about 285 C., but below'the boiling point of the triphenyl phosphite andthe octyldicresyl phosphonate for a period of about 1 to 10 hours.
- chlorobenzene is continuously distilled from said reaction mixture. Generally when no furtherchlorobenzene comes off, the reaction is substantially complete.
- the clear, straw liquid was, washed twice with 500 ml. water portions, keeping the temperature below 25 C. This was followed by first washing with 500 ml. of 5% sodium hydroxide solution, and then with 500 ml. of 5% potassium hydroxide, in 50% aqueous ethanol. The organic layer was then washed with 500 ml. water portionskuntil neutral (3 times). The ethylene dichloride was removed by vacuum stripping under wateraspirator vacuum to 100 C. at 37 mm., leaving 581 g. of pale yellow residue.
- The-trialkylaluminum hydrocarbon solvent plus some residual xylenol were distilled off by heating to 168 C. under vacuum in a one-liter flask having a capillary nitrogen ebullator.
- the distillate was collected from 44 C. (1.0 mm.) to 82 C. (0.6 mm.). It weighed 78.0 g. (theoretical weight of AlR solvent is 103 g.) and had a cresolic odor.
- the cold trap condensate weighed 8.2 g. (total condensate 86 g.).
- the residual crude product was a hazy, straw oil, weighing 494.3 g. (84% yield); It contained 0.7% chlorine.
- EXAMPLE II An alkyl phosphonate diester prepared as described in the first portion of Example I was treated with triethyl phosphite at a temperature of about 150 C. without substantial reduction of the chlorine content.
- a process for the substantial removal of a halogen selected from the group consisting of chlorine, bromine and iodine from an alkyl phosphonate diester containing as a contaminant corresponding haloalkyl phosphonate diester which comprises treating the contaminated mixture at a temperature of a least about 200 C.
- a process for the substantial removal of a halogen selected from the group consisting of chlorine, bromine and iodine from an alkyl phosphonate diester containing as a contaminant up to about by weight of a corresponding haloalkyl phosphonate diester which comprises admixing with said contaminated mixture at least a stoichiometric amount, based upon the quantity of contaminant, of a phosphite triester having a boiling point of at least 200 C.; maintaining the resulting mixture in the liquid phase at atmospheric pressure and at a temperature of at least 200 C.
- a process for the substantial removal of chlorine from a mixed monoalkyl dicresyl phosphonate containing as a contaminant about 10% by weight of corresponding haloalkyl dicresyl phosphonate which comprises admixing with said mixture at least a stoichiom'etric amount, based upon the amount of haloalkyl dicresyl phosphonmate, of triphenyl phosphite; maintaining the resulting mixture in the liquid phase at atmospheric pressure at a temperature of about 280 C. for a period of about 4 hours; and distilling from said reaction mixture during said period, chlorobenzene.
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Description
United States Patent 06 3,335,205 Patented Aug. 8, 1967 ice 3,335,205 PHGSPHONATE PURIFICATION PROCESS (Ilarence W. Hutfrnan, Glenview, Ill., assignor to International Minerals & Chemical Corporation, a corporation of New York No Drawing. Filed May 27, 1964, Ser. No. 370,660 3 Claims. ((11. 260-990) This invention relates to a process for the purification of organic phosphonates. In a more specific aspect, this invention relates to a process for the purification of alkyl phosphonate diesters contaminated with halogen-containing impurities. In a preferred aspect this invention relates to a method for removing chlorine from a monoalkyl phosphonic acid diester containing as a contaminant corresponding chloromonalkyl phosphonic acid diester.
The use of organic phosphorus compounds, such as tricresyl phosphate, or alkyl phosphonates such as decyl dicresyl phosphonate, as plasticizers for polymeric films and resins is well known. It is also known that materials useful as plasticizers should be free from halogen contamination since this halogen has a strong tendency to cause discoloration or yellowing in the plasticized polymer. This problem is especially important when the plasticized polymer is white or clear.
In co-pending application, Serial No. 223,511, filed September 13, 1962 by Huifman et al., entitled Process for the Production of Monoalkyl Phosphonic Acid Diesters, Diamides and Dihalides, now US. Patent 3,149,- 144, granted September 15, 1964 there is described a new and improved process for the production of monoalkyl phosphonic acid diesters which involves as an intermediate step halogenation of an intermediate monoalkyl halophosphine to raise the valence of the phosphorus therein from the trivalent to the pentavalent stage. Although great care is usually exercised in this halogenation procedure, as for example, by controlled addition of halogen at low temperatures, it has been difiicult, if not impossible, to prevent some halogen from reacting with a carbon atom in the alkyl group of the monoalkyl halophosphine intermediate as well as with the phosphorus therein. This undesirable halogenation usually occurs on the carbon atom alpha to the phosphorus atom since this carbon atom is the most reactive. The undesirable halogenated compound follows through the process as a whole and is usually present in the final monalkyl phosphonic acid diester product as the corresponding halomonoalkyl phosphonic acid diester. Because of the close boiling points between the desired compound and its halo analogue, it has been impossible to effectively separate the two by distillation procedures. Further, numerous well-known chemical methods for the removal of halogen proved inefifective. Thus, for example, the use of such materials as sodium acetate, epoxides, lead oxide, lead tetraacetate, potassium borohydride, sodium methoxide and magnesium amalgam were all ineffective.
In accordance with the present invention I have discovered that monoalkyl phosphonic acid diesters contaminated with corresponding chloromonoalkyl phosphonic acid diesters can be substantially dehalogenated and made suitable for use as plasticizers by treatment with phosphite triesters, as more particularly described hereinafter. While phosphites have been used directly as antioxidants and stabilizers for polymeric resins, it was not at all apparent that these materials would be effective for the purpose herein intended, especially since one of the most reactive commercial phosphite triesters, triethyl phosphite, proved ineffective.
It is, therefore, an object of the present invention to provide a process for the purification of alkyl phosphonate diesters contaminated with halogen-containing impurities.
It is a further object of this invention to provide a method for removing halogen from a monoalkyl phosphonic acid diester containing as a contaminant corresponding halomonoalkyl phosphonic acid diester.
It is a specific object of the present invention to provide a method for removing chlorine from monoalkyl dicresyl phosphonate containing as a contaminant chloromonoalkyl dicresyl phosphonate.
Additional objects of the present invention will be apparent from the description which follows.
In general, the present invention is concerned with a process for the substantial removal of a halogen selected from group Cl, Br and I from an alkyl phosphonate diester containing as a contaminant corresponding haloalkyl phosphonate diester which involves treating the contaminated alkyl phosphonate diester in the liquid phase, preferably at atmospheric pressure, at a temperature of at least 200 C. for a period of from about 1 to about 10 hours, with at least a stoichiometric amount, based upon contaminant, of a phosphite triester having a boiling point higher than the temperature at which treatment is effected. During said treatment there is distilled from the reaction mixture a halogen-containing compound that boils under the ambient conditions of the treatment.
It is believed, although applicant does not want to be bound by the theory, that the chemistry of his process proceeds according to the equation In the above equation the formula designated '1. represents the monoalkyl phosphonate diesters which are to be purified and which may be prepared as described in copending application Serial No. 223,511 referred to hereinbefore. The formula designated II represents the contaminant, or corresponding halomonoalkyl phosphonate diester. Thus, I and II represent the mixture treated in accordance with the process of the present invention. The formula designated III represents the phosphite triester which reacts with the halogen-containing contaminant in what is believed to be an Arbuzov-type reaction. The selection of the appropriate phosphite triester is an important feature of the present process, as will be explained more fully. Formula IV represents one of the products resulting from the reaction between II and III and can be classed generally as an alkyl ibisphosphonate diester. If desired, this product can be separated from I by distillation or the like. However, IV is also a phosphonate and it can be retained in admixture with I for use as a plasticizer, since the deleterious halogen has been removed. Formula V represents the organic halide by-product resulting from the reaction between II and III. Product V preferably should be removed by volatilization from the reaction mixture as it forms. If V is an alkyl halide, it, too, would react with the phosphite triester in an Arbuzov reaction, and, thus, interfere with the desired reaction. If V is an aromatic halide, it will not undergo the Arbuzov reaction and need not be removed as it forms. However, it must eventually be removed from the product by volatilization.
In Formulas I, II and IV, R is an alkyl hydrocarbon radical having from 1 to 23 carbon atoms. Examples of the alkyl radicals include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and eicosyl. It will be appreciated, of course, that the alkyl phosphonate diester may be a mixture wherein R may be of varying lengths since; as pointed out in the co-pending application, SerialNo. 223,511, this portion of the. molecule comes from the alkyl groups contained in trialkyl aluminum which may be the same or different. X in Formulas Hand V is a halide selected from the group consisting of chlorine, bromine and iodine. Thepreferred and most common halide is chlorine. R in Formulas I, II and IV is an organic radical selected from the group consisting of aliphatic hydrocarbon, cycloaliphatic hydrocarbon, aromatic hydrocarbon, mixed aliphatic-aromatic hydrocarbon such as alkaryl and aralkyl groups and alkyl oxyalkylene. The above hydrocarbon radicals may besaturated or unsaturated and substituted or unsubstituted, but when substituted they must be substituted with inert functional groups, that is, those groups which will not interfere with the reaction between the halogen impurity and the phosphite triester. Illustrative examples of R groups include methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, and the like; olefinic and acetylenic analogues of the foregoing; cyclohexyl, cyclopen tyl, methylcy'clohexyl, phenyl, methylphenyl, ethylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, tolyl, xylyl, methoxyethyl, ethoxyethyl, methylpolyoxyethyl, methoxypropyl, eth lpolyoxypropyl, and the like. Typical products represented by Formula I include ethyl dicresyl phosphonate, octyl dicresyl phosphonate, ethyl dioctyl phosphonate, octyl diphenyl phosphonate, pentyl dibutyl phosphonate and the like. Obviously, from the preceding description, Formula II represents cor-responding compounds having a halogen attached to the carbon atom alpha to the phosphorus atom in the phosphonate diester.
Eormula III represents the phosphite triester employed in the process of the present invention. As mentioned earlier herein, this phosphite triester must be carefully chosen. That is, it must have a boiling point higher than about 200 C. and above the temperature at which the process is employed. Further, it must contribute a radical, R", which when combined with the halide, X, results in a product which boils below the temperature at which the process is carried out. Thus, in the formula P(OR") R" is an organic radical selected from the group consisting of aliphatic hydrocarbon, cycloaliphatic hydrocarbon and aromatic hydrocarbon. All of the R" may be different or alike, but in any event, the triphosphite ester must meet.
the two major criteria set forth above. The preferred phosphite triester is triphenyl phosphite. Typical phosphites which may be employed include trioctyl phosphite, tricresyl phosphite, octyldicresyl phosphite, ethyldiphenyl phosphite, ethyldicresyl phosphite, octylnonyldecyl phosphite, diphenylcresyl phosphite, ethyldinaphthyl phosphite, octyldicyclohexyl phosphite, and the like. 'Phosphite esters are, in general, prepared by treating hydroxyl-containing organic compounds such as alcohols, phenols, etc., with phosphorus trihalides such as PCl 'PBr3 and P1 Given the foregoing criteria, the choice, of a proper phosphite triester for the present process is within. the skill of an ordinary chemist. Triphenyl phosphite is preferred because of its ready availability and the fact that the chlorobenzene which forms, will not undergo the Arbuzov reaction.
In carrying out the process of the present invention, solvents may be employed, but they are generally not preferred since they tend to diminish the reaction rate by the dilution factor involved. However, if solvents are employed, they should be high boiling, viz, boil in excess of 200 C. and be inert in the environment.
The process of the present invention is preferably carried out at atmospheric pressure, although higher or lower pressuremay be employed provided the reactants are kept in the liquid phase and the temperature is maintained above about 200 C. and may go as high as the boiling pointof the lowest boiling reactant. The process may be carried out over a period of about 1 to about hours. It will be appreciated that the nature of the material being treated and. the choice of reactants will have a bearing, within the limits above prescribed, .on the conditions to be employed in carrying out the process.
In a preferred embodiment of the present invention, an 1 alkyl phosphonate diester containing as a contaminant an amount, up to about 40% by weight, preferably between about 5 and about 10% by weight of corresponding haloalkyl phosphoate diester is admixed with at least a stoichiometric amount, based upon the amount ofcontaminant of a phosphite triester having a boiling point of at least about 200 C. Typically, the alkyl phosphonate diester can be octyldicresyl phosphonate containing chlorooctyldicresyl phosphonate as a contaminant and the phosphite triester can be triphenyl phosphite. The mixture is maintained in the liquid phase at atmospheric pressure and at a temperature of at least 200 0, preferably about 285 C., but below'the boiling point of the triphenyl phosphite andthe octyldicresyl phosphonate for a period of about 1 to 10 hours. During said time chlorobenzene is continuously distilled from said reaction mixture. Generally when no furtherchlorobenzene comes off, the reaction is substantially complete. I
The following examples will help illustrate the underlying principles of the present invention.
EXAMPLE I Preparation 0 alkyl phosphonate diester Mixed alkyl trialkylaluminum, 69% solution in a hydrocarbon solvent, 332.0 g. (0.47 mole), dissolved in ml. of ethylene'dichloride, was added to a solution of phosphorus trichloride, 230.8 g. (1.68 moles), in 500 ml. of ethylene dichloride in a three liter flask. The addition was carried out over a one-hour period at 35 to 45 C. under nitrogen. The reactants were heated an additional one hour at the same temperature and the clear, pale-yellow solution cooled by means of a Dry Ice-acetone bath to 5 C. The theoretical quantity of chlorine, 119 g. (l.68 moles) was bubbled in at 0 to, 5 C. at 210 ml. per minute (5.0 units, Flowrator 02F-1/8-12- 5/36) for 180 minutes with the hood light off. The cold bath was removed and isopropanol, 85.8 g. (1.43 moles), was added in 15 minutes, during which time the tempera- I ture gradually rose to 30 C. and hydrogen chloride evolved. The mixture was then heated at 35-45" C. for /2 hour. Jefferson Lake .Sulfur Company Oresols No. 23, 469.0 g. (4.28 moles, 20% excess), were added in 20 minutes at 40 to 50 C. and the solution wasthen heated at reflux for 5 hours. The clear, straw liquid was, washed twice with 500 ml. water portions, keeping the temperature below 25 C. This was followed by first washing with 500 ml. of 5% sodium hydroxide solution, and then with 500 ml. of 5% potassium hydroxide, in 50% aqueous ethanol. The organic layer was then washed with 500 ml. water portionskuntil neutral (3 times). The ethylene dichloride was removed by vacuum stripping under wateraspirator vacuum to 100 C. at 37 mm., leaving 581 g. of pale yellow residue.
The-trialkylaluminum hydrocarbon solvent plus some residual xylenol were distilled off by heating to 168 C. under vacuum in a one-liter flask having a capillary nitrogen ebullator. The distillate was collected from 44 C. (1.0 mm.) to 82 C. (0.6 mm.). It weighed 78.0 g. (theoretical weight of AlR solvent is 103 g.) and had a cresolic odor. The cold trap condensate weighed 8.2 g. (total condensate 86 g.). The residual crude product was a hazy, straw oil, weighing 494.3 g. (84% yield); It contained 0.7% chlorine.
Purification of alkyl phosphonate diester The remainder of the crude product 478.8 g., was treated with triphenyl phosphite,-31.4 g. (0.10 mole, 10% excess based on chlorine content), at 275-285 C. for 3 hours, with nitrogen bubbling through the solution. During this time, 14.1 g. of material distilled over, at a maximum vapor temperature of C. The distillate (which should be mainly chlorobenzene, [1. 132 C.) was collected in two fractions, both having a phosphonite odor and giving positive Beilstein tests for chlorine; 1st cut: 11. 1.5209; 2nd cut: n 1.5193. The residual treated product contained 0.1% chlorine. The very hazy, orange dechlorinated product, 479 g., was distilled in a molecular still (Rodney Hunt Vacu-Film Processor) at 190-205 C. at 15-19 a. The very pale yellow distillate weighed 436.1 g. (76% yield). Analysis: Chlorine, 0.1%; acid No. 1.3. The product was dissolved in 500 ml. of benzene and re-washed with 200 ml. of 5% potassium hydroxide in 50% aqueous ethanol. After washing with water until neutral and vacuum stripping, the acidity of the material was determined. Analysis: Acid No. 0.25.
EXAMPLE II An alkyl phosphonate diester prepared as described in the first portion of Example I was treated with triethyl phosphite at a temperature of about 150 C. without substantial reduction of the chlorine content.
EXAMPLE III Dicresyl alkyl phosphonates prepared as described in the first portion of Example I were treated by various conventional methods for the removal of chlorine as well as the method in the present invention. The results of said tests are set forth in Table III.
TABLE III [Dichlorination of dicresyl alkylphosphonates] Treatment Percent Chlorine Reagent Temp., Time, Initial Final 0. hrs.
Steam 100 0.5 0.7 0. 7 Sodium acetate. 170 1 0.7 0. 7 Admex 710.. 140 1 0.7 0. 7 Lead Oxide- 85 1 0. 7 0.7 Do 170 1 0 8 0.4 Lead Tetraacetate. 85 1 0.7 0.7 Potassium Borohydride 40 1 0.5 0.5 Sodium Methoxide 65 4 0.5 0.5 Magnesium Amalgam 35 8 1. 2 1. 2 Triphenyl Phosphitm. 280 2 0.7 0.2 Do 280 3 0. 7 0. 1 Triethyl Phosphite 150 2 0.6 0.5
While this invention has been described and exemplified in terms of a preferred embodiment, those skilled in the art will readily appreciate that variations can be made without departing from the spirit and scope of the invention.
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for the substantial removal of a halogen selected from the group consisting of chlorine, bromine and iodine from an alkyl phosphonate diester containing as a contaminant corresponding haloalkyl phosphonate diester which comprises treating the contaminated mixture at a temperature of a least about 200 C. while maintaining said mixture in the liquid phase for a period of from about 1 to about 10 hours with at least a stoichiometric amount, based upon the amount of contaminant, of a phosphite triester having a boiling point higher than the temperature at which said treatment is eltected; and distilling from said reaction mixture during said treatment a halogen-containing compound having a boiling point lower than the boiling point of said alkyl phosphonate diester and said phosphite triester.
2. A process for the substantial removal of a halogen selected from the group consisting of chlorine, bromine and iodine from an alkyl phosphonate diester containing as a contaminant up to about by weight of a corresponding haloalkyl phosphonate diester which comprises admixing with said contaminated mixture at least a stoichiometric amount, based upon the quantity of contaminant, of a phosphite triester having a boiling point of at least 200 C.; maintaining the resulting mixture in the liquid phase at atmospheric pressure and at a temperature of at least 200 C. but below the boiling point of said phosphite triester and said alkyl phosphonate diester for a period of from about 1 to about 10 hours; and distilling from said reaction mixture during said period a halogencontaining compound having a boiling point below the ambient temperature of said reaction mixture.
3. A process for the substantial removal of chlorine from a mixed monoalkyl dicresyl phosphonate containing as a contaminant about 10% by weight of corresponding haloalkyl dicresyl phosphonate which comprises admixing with said mixture at least a stoichiom'etric amount, based upon the amount of haloalkyl dicresyl phosphonmate, of triphenyl phosphite; maintaining the resulting mixture in the liquid phase at atmospheric pressure at a temperature of about 280 C. for a period of about 4 hours; and distilling from said reaction mixture during said period, chlorobenzene.
No references cited.
CHARLES B. PARKER, Primary Examiner. A. SUTTO, Assistant Examiner.
Claims (1)
1. A PROCESS FOR THE SUBSTANTIAL REMOVAL OF A HALOGEN SELECTED FROM THE GROUP CONSISTING OF CHORINE, BROMINE AND IODINE FROM AN ALKYL PHOSPHONATE DIESTER CONTAINING AS A CONTAMINANT CORRESPONDING HALOALKYL PHOSPHONATE DIESTER WHICH COMPRISES TREATING THE CONTAMINATED MIXTURE AT A TEMPERATURE OF A LEAST ABOUT 200*C. WHILE MAINTAINING SAID MIXTURE IN THE LIQUID PHASE FOR A PERIOD OF FROM ABOUT 1 TO ABOUT 10 HOURS WITH AT LEAST A STOICHIMETRIC AMOUNT, BASED UPON THE AMOUNT OF CONTAMINANT, OF A PHOSPHITE TRIESTER HAVING A BOILING POINT HIGHER THAN THE TEMPERATURE AT WHICH SAID TREATMENT IS EFFECTED; AND DISTILLING FROM SAID REACTION MIXTURE DURING SAID TREATMENT A HALOGEN-CONTAINING COMPOUND HAVING A BOILING POINT LOWER THAN THE BOILING POINT OF SAID ALKYL PHOSPHONATE DIESTER AND SAID PHOSPHITE TRIESTER.
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